Propylene-(1, 2)-bis-dithiocarbamates



United States Patent 3,326,951 PROPYLENE-(1,2)-BlS-DITHIOCARBAMATES Hellmuth Lehmann, Wuppertal-Elberfeld', Ferdinand Grewe, Burscheid, and Walter Lautenschlager, Wuppertal-Vohwinkel, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a German corporation No Drawing. Filed Feb. 20, 1963, Ser. No. 260,037 Claims priority, application Germany, Mar. 1, 1962, F 36,152 4 Claims. (Cl. 260-439) The fungicidal activity of alkyl-bis-dithiocarbamic acid salts of alkali metals, alkaline earth metals and heavy metals has been known for a long time. Thus for example in US. Patent No. 2,317,765 fungicidally active mixtures are claimed which contain, as active ingredient, the di-sodium, cupric or ferric salt of ethylene-bis-dithiocarbamic acid.

Furthermore in Austrian patent specification No. 193,- 891, disodium, cupric and zinc propylene-bis-dithiocarbamates are described as substances active against plantpathogenic fungi.

Finally the published documents of South African patent application No. 60/5,l25 relate to fungicidal compounds based on zinc and calcium salts of ethylene-bis dithiocarbamic acid whose ethylene bridge is monoor disubstituted by monovalent aliphatic radicals, zinc propylene-, ethyl-ethyleneand dimethylethylene-bisdithiocarbamates being mentioned as especially effective.

It has now been found that the propylene-(1,2)-bisdithiocarbamic acid salts not hitherto described in the literature, of barium, strontium, magnesium, nickel and cobalt, as well as of diand tri-valent iron, possess outstanding fungicidal properties.

These compounds are especially suitable for combating fungus disease activators but distinctly excel over the known ethyleneor propylene-bis-dithiocarbamates in this respect. Thus for exampleas may be seen in detail from the enclosed tables-ferrous as well as ferric propylene-bis-dithiocarbamate is distinguished, from the corresponding zinc and iron salts of ethylene-bis-dithiocarbamic acid as well as from zinc propylene-bis-dithiocarbamate, by a significantly superior activity, while barium and magnesium propylene-bis-dithiocarbamate are not .only strongly active fungicides but also considerably better tolerated by plants than the known calcium propylenebis-dithiocarbamate. Apart from these advantages the nickel salt of propylene-bis-dithiocarbamic acid possesses a further special and technically valuable effect.

The said compound not only distinctly excel over the zinc ethylene-bis-dithiocarbamate known as a standard fungicidal preparation when used against Phytophthora infestans on tomatoes under greenhouse conditions, but is furthermore strongly activated when outside, the activation increasing with increasing intensity of illumination and exposure time on the plant, so that in open conditions, nickel propylene-bis-dithiocarbamate possesses a better fungicidal activity than the corresponding zinc salts of ethyleneand propylene-bis-dithiocarbamic acid. This positive influence of weather conditions was in no way to be foreseen. It arises presumably from a destabilising effect, which can be confirmed by experiments in vitro.

The production of the propylene-bis-dithiocarbamic acid salts to be used according to the invention is carried out by methods known in principle by reaction of propylene diamine (1,2-diaminopropane) with carbon disulphide in the presence of a strong base, preferably the aqueous solution of an alkali metal or ammonium hydroxide followed by precipitation of the soluble propylene-bis-dithiocarbamate formed with an aqueous solution of the alkaline earth or heavy metal salt concerned.

Patented June 20, 1967 See wise to this solution and the reaction mixture is then treated with 555 g. of 46% sodium hydroxide solution. The solution of propylene-bis-dithiocarbamic acid sodium salt obtained is precipitated,

(a) with a nickel sulphate solution, whereby 960 g. of nickel propylene-bis-dithiocarbamate are obtained, or (b) with a ferrous sulphate solution, whereby ferrous propylene-bis-dithiocarbamate is obtained in a yield of On account of their outstanding fungicidal properties, the agents of the present invention are suitable for combating all those phytopathogenic fungi against which hitherto the abovementioned known ethyleneor propylene-bis-dithiocarbamates have been applied, i.e. primarily against Phytophthora infestans, Cladosporium fulvum, or Alternaria solani on tomatoes and potatoes, against Peronospora (Plasm opara viticola) on vines, Venturia inaequalis on stone fruit as well as against other fungoid pests on various cultivated plants. Ferrous propylenebis-dithiocarbamate has moreover proved especially effective against grain rust, while the corresponding nickel salt comes in consideration especially for combating leaf spot disease on tea.

The application of the compounds according to the invention as fungicides proceeds in ways known in principle, i.e. preferably in combination with suitable solid -or liquid extenders or diluents. As solid carriers, chalk,

silica gel, kieselguhr, talc, bentonite, and the like are chiefly to be considered, while for the production of liquid formulations Water is especially applied as diluent. Since the propylene-bis-dithiocarbamates to be employed according to the present invention are however to a great extent water-insoluble, it is expedient in making aqueous dilutions, and indeed sometimes necessary, first to dissolve the agent in question in a solvent aid such as acetone or dimethyl formamide and to dilute this preliminary mixture with water in the presence of a commercial nonionic emulsifier as well as optionally with the use of wetting, adhesive or solid formulation aids, to the concentration of active agent desired in any given case.

The employment of the agents according to the invention in combination with other fungicides and/or insecticides is possible.

The following examples are given to illustrate the invention.

(a) Determination of the fungicidal activity against Phytophthora infestans on tomatoes.

Young tomato plants of the Bonny Best are sprayed at the 4- to S-leaf stage with aqueous emulsions or suspensions of the preparations mentioned below. The plants are then allowed to drain off for 24 hours, sprinkled with a spore suspension of Phytophthora infestans and then brought into a moist chamber in which a relative humidity of about prevails. After the incubation period has passed, the fungus infestation rate is determined by evaluating the individual feather-leaves, values of 0 (no infestation) to 5 (leaf infested on' the whole surface by fungus, or destroyed) being set up and the degree of infestation expressed as a percentage of the infestation of the untreated control plants (=100) (b) Test of the fungicidal activity when employed against Plasmopara viticola on vines.

3 Young pot vines of the type Muller-Thurgau are inoculated 24 hours after the application of each of the preparations mentioned below in analogous manner to that used in the experiments with Phytophthora infestans,

TABLE 5 [Test fungus: Phytophthora i/nfesta'ns on tomatoes (expt. in the open)] with spores of Plasm'opara viticola. The evaluation of the 5 Active agent Infestation rate in concentrapercent on tests proceeds as described under a). Preparation mm m The results obtained in the indlvidual series of expercent periments with the difierent test fungi are listed in the following Tables 1 to 7.

Fungicidal activity of the ferrous, ferric, barium and 10 g igggggg blsdlthlo 4 4 32 magnesium salts of the propylene-bis-dithiocarbamic acid Zinc-propylene bisdithio- 0.15 9 1o 35 in comparison with zinc and calcium propylene-bis-dithiog iggfi gf bisdithim M 10 73 carbamates as well as with zinc and ferrous ethylenecarbamate. bls'dlthlocarbamates: Controls (untreated) 32 71 97 1 Amount employed 1,0001. broth per hectare.

TABLE 1 TABLE 6 [Test fungus: Plm t ophthom infestcms on tomatoes] [Test fungus: Phytophthora infestans on tomatoes] I f ti 1 on n Infestationln Active Percent Active agent percent of the Preparation concentration untreated Preparation concentration untreated 111 Percent controls in percent controls pen-ousmmpylene blsditmoearbamtgun @0125 0 Barium-propylene bisdithiocarbamate 0.025 0 g Magnesium-propylene bisdithiocarba- 0. 025 0 1 i ma 9. Zmc pmpy ene blsdlth ocarbamate Calcium-propylene bisdithiocarbamate. 0.025 0.0 Zinc-ethylene blsdithiocarbamate-.. 0031 59 Zinc ethy1ene bisdithiocarbamflte 8- Table 7 shows plant tolerance* of the barium and mag- TABLE 2 nesium propylene-bis-dithiocarbamates in comparison 4 with propylene-bis-dithiocarbamic acid calcium salt. [Test fungus: Plasmopara Vtttcola on vines] TABLE 7 Iniestion in Active agent percent of the [Test plant. Dwarf beans (Saxa)] Preparation concentration untreated in percent controls Active agent (=100) concentration 7 Preparation Ferrous-propylene bisdithiocarbamate 0. 0008 19 Ferrous-ethylene bisdithiocarbamate 0.0008 39 3% 0.15%

Barium-propylene bisdithiocarbamate. I O Magnesium-propylene bisdithiocarbamate II I Calcium-propylene bisdithiocarbamate III II TABLE 8 [Test fungus: Phytophthora, mfestwns on tomatoes] P the above tapleslt Clear that ferrous femc or nlckel propylene-bis-dithiocarbamates when employed Intimidation against Phytophthorzr infestans on tomatoes clearly excel P r u n g g i figa g fig with respect to fungicidal activity the known Zinc salts 5 O in percent untreated of ethylene-and propylene-bis-dithiocarbamic acid. Moreg ga f over the given experimental results clearly show the unquestionable superiority of the ferrous propylene-bisdithioc rbarnate in com arisen to the orres 0 din eth l- Ferric-propylene bisdithiocarbamate 0.0062 0 b P l PIP n g Zinc-Propylene bisdithiocarbamate (1025 0 6116 Is- 1t.1ocar {fume ac! Sa t agamst .f yi 383g cola on vines. Fmally the superior fungicidal activity llm-ethylwe bisdithiocarbamate 010062 26 of propylene-bis dithiocarbamic acid barium and magnesium salts compared with the corresponding 7 known calcium salt is clearly apparent, as well as the better plant toleration of the two first mentioned compounds. We claim: TABLE 4 1. The bis-dithiocarbamic acid metal salt of a com- [Test fungus: Phytophthora infestans on tomatoes pound h i th f r l (greenhouse experiments)] Infestation P t Activetagent rate; infpefi- CH3 OH NH G SH repara ion concen ration cen o e in percent untreated CH2 NH SH controls (=100) 0 025 7 the metal thereing being a member selected from the Nickel-propylene bisdithiocarbamate 0: 0032 21 group (zonslstmg of stronuum, and cobalt g. 4g 2. Cobalt propylene-( 1,2) -b1s-d1th1ocarbamate. Zinc-ethylene bisdithiocarbamate 0: 0032 48 0.0008 76 The evaluation took place 4 days after spraying. Degrees of merit from O to V were attributed (O withoirt damage;

V :plant dead).

5 6 3. Strontium propy1ene-(1,2)-bis-dithiocarbamate. 3,082,229 3/ 1963 Nash 260-455 X 4. Nickel propylene-(1,2)-bis-dithiocarbamate. 3,085,043 4/1963 Beaver et a1. 16722 FOREIGN PATENTS 5 193,891 12/1957 Austria.

References Cited UNITED STATES PATENTS ,31 35 92: l l CHARLES B. PARKER, Primray Examiner.

2, 74,0 2 3 19 CO iIlS 16 22 2,983,747 5/1961 Campbell et al' 260 455 JULIAN S. LEVITT, JOSEPH P. BRUST, Exammers. 3,012,053 12/1951 Lesslie 260455 GEORGE A. MENTIS, DALE R. MAHANAND,

3,039,918 6/1962 Hambsch et a1. 167-22 10 AssistantExamz'ners. 

1. THE BIS-DITHIOCARBAMIC ACID METAL SALT OF A COMPOUND HAVING THE FORMULA 